Compounded mineral oil



Patented Aug. 14, 1945 2,382,043 COMPOUNDED MINERAL 01L Bruce B. Farrington, James 0. Clayton, and John '1. Rutherford, Berkeley, Calif., assignors, by

mesne assignments, to California Research Corporation, San Francisco, Calif., a corporation of Delaware No Drawing. Application January 13, 1941, Serial No. 374,241, which is a division of application Serial No. 241,648, November 21, 1938. Divided and this application January 4, 1943, Serial No.

471,276 8 Claims.

This invention relates to a new and useful composition of matter and involves a composition comprising a viscous hydrocarbon oil and polyvalent metal salts of certain substituted acids of phosphorus.

This application is a division of our application Serial No; 374,241, filed January 13, 1941, issued June 15, 1943 as Patent N0. 2,321,804, which in carbon oils to deteriorate or partially decompose and oxidize when subjected to high temperatures. This deterioration is evidenced by the deposition of adhesive deposits on hot metal surfaces over which the hydrocarbon oil may flow. It is importantthat resistance to such deterioration be imparted to hydrocarbon oils, particularly to lubricating oils, in order that such compositions maybe relatively free from the tendency to form such deposits even under high temperatures and severe operating conditions. A direct'result of this type of deterioration during lubrication of internal combustion engines, such as engines of the Diesel type, is the tendency of the oil to cause or permit the sticking of piston rings.

The crankcase lubricant'in internal combustion engines is subjected to extremely severe operating conditions and in engines of the Diesel type the lubricant encounters in the piston ring zone temperatures of from approximately 425 to 650 F, and pressures from the oxidizing combustion gases as high as 750 to 1150 lbs. persq. in. 'Addition agents which render hydrocarbon oils resistant to deterioration by heat at high temperature levels in the order of those above mentioned usually impart to the oil the ability to inhibit piston [sticking ,in internal combustion enines permit longer periods of operation of such engines'without the necessity of major overhauls heretofore occasioned by stuck piston rings.

It should be noted that stabilizing agents which are eifective at low temperatures to impart increased stability to hydrocarbon oils, orwhlch are eilective at temperatures even as high as 200 or 250 F., are often ineflective under the more severe operating conditions and higher temperature levels to which lubricating oils are subjected in Diesel engines. Thus the operativeness of a stabilizer at atmospheric temperatures, or even temperatures as high as 200 to 300" F., gives no adequate basis for predicting the action of the same stabilizing agent at materially higher temperatures and under more severe operating conditions. The disclosures in the prior art relative to such stabilizers therefore cannot serveas a guide for one seeking stabilizing agents or oxidation inhibitors eilective at higher-temperature levels. The phenomena involved are catalytic in nature, are highly empirical and require extensive experimentation to determine the action of a given type of addition agent.

The present invention involves the discovery that dispersion of polyvalent metal salts of substituted oxyacids of phosphorus in hydrocarbon oils such as mineral lubricating oil imparts new, unpredictable and highly desirable properties to the composition. These. new properties render the compounded oil particularly useful for various purposes. Although increased resistance to deterioration at high temperature levels comprises one of the principal advantages of the compounded oils of thisinvention, it is to be understood that the invention is not limited to this feature, that different compounds of the general type herein involved vary in their degree of effectiveness and may impart one or more other desirable properties to the lubricating composition. For example, certain of the compounds reduce the amount of wear produced as compared with a straight uncompounded mineral oil. The same or other compounds inhibit the corrosion of copp r-lead or cadmium-silver bearing metals, etc. In general, however, it has been discovered that the new compositions herein disclosed are more stable to heat than is a hydrocarbon oil with which the compositions are compounded. The new compositions of this invention are therefore useful where resistance to deterioration by heat is important. An example of such utility, other transfer fluid where it may be desirable to inhibit or prevent the formation of a deposit on the metal surfaces from or to which heat is being conveyed. Likewise, the increased resistance to oxidation imparted to the .oil by the compounds of this invention will find various applications as, for instance, in an insulating, switch, or transformer oil.

It has also been discovered that certain metal salts of substituted oxyphosphoric acids have a combination of properties heretofore unknown and particularly desirable in compounded mineral oil, namely, the ability to inhibit oxidation and impart to lubricating oils increased resistance to deterioration by heat, the ability to inhibit piston ring sticking, freedom from the production of increased wear on cylinder walls and piston rings as compared with uncompounded mineral oils, and low corrosivity as respects the chemical actlonoithecompotmdedollonbearingmetals' such as cadmium-silver and copper-lead alloys. Although various compounded mineral oils are known whicharecapabletoinhibitingpistonrlng sticking, the discovery of specific compounding agents capable of imparting the above combinationoipropertiestohydrocarbonollsrepresents an unobviom and important contribution.

Metalsaltsoimbstitutedoxyacidsotphosphoruswhlchmay be addedtohydrocarbonlubricatins oils to provide anew composition of -matteroi'thetypehereininvolvedcomprisethe saltsoimetalsselectedtromgroupsmmlv and VI of Mendelyeevs Periodic Table of the Eleminum, calcium, barium, strontium, chromium and magnesium. Salts of iron, cobalt, nickel, sine, tin and lead comprise additional examples of compounds iallingwithmthe'broader aspects of the invention.

'lhe metal salts of this invention are preferably I formed from substituted oxyacids of pentavalentphosphorus?! the following t pe formulae:-

oa oa 0=P or o=r--on' 06 0H 011 where R and R may be alhl, aryl, alkaryLaralkyi or cyclic old radicals. Substituted phosphoric acids containing at least twelve carbon atoms are preferred. Examples of preferred type acids are alkyl or alkaryl substituted phosphoric acids having at least twelve carbon atoms in the molecule. However, it is to be understood that the broader aspects of the invention include theuseoi'othertypesoisubstimtedoxyacldsoi phosphorus containing more than twelve carbon atoms. Additional examples or substituted oxyacids of phosphorus which may be usedin forming the metal salts of the present invention are as follows:

InalloitheaboveicrmulaeRandR'maybe flmaryLalkaryLaralkylorcyclicd srwps. v

In 90187816111; metal salts of substituted 'ments. Speciflcoimchmetalsarealuphate, calcium naphth'enyl phosphate, chromium phate, andgbarlum naphthenyl PM Additional examplesoisaltswithinthesccpeot the invention are: aluminum di-cyclohexanyl Phosphate, aluminum dil phosphate, aluminum I -I? u 1 a m phate, aluminum di-(G-chloro, 2- phenyi) phosphate, aluminum di-(S-methyl. 4 -chloro pheno P os ate, calciumdiphos- Pila e, calcium di-stearo-giyceryl phosphate, calcium tetra-chloro octadecyl phosphate, calcium -P vl' chum) calcimn di-(3-methy1. 4-chloro phenyl) phosphate. chromium di-cyclohexanul phosphate, chromium di-stearmglyceryl phosphate, chromium tetrachloro-octadecyl phosphate, chromium di-(6'-- chloro, Z-phenyl phenyl) nh sphataehromlum di-(3-methyl, 4-chloro phenyl) phosphate, msgneslum di-cyclohexanyl P l-stearo-sly ml pho phate,

D spha chloro, 'a-phmyl m1) phosph te. masuesimn 181. 4-chlpro M) magnesiumlwrylphosphateceiwlphos pha octadecylrimsphatamasnesh mm m hos h te.

, phate, um spermenyl phosphate. masderlvatives oioxyacidsotphosphomssuchas' acid, HaPOi; HsPOa: orthophosphorlcacld. HaPOs; Dymphosmadame-10'; all withhithebroadeataspectsottheinvention. By"suhsiitutedcrs|fl stltuted derivatives of" acids oiphos horus wheneverwedheremitisintcndedtodesisnateaclds containing anorg anicmoithetymprevkmslylisted,i.e.,alky ,aryl,alkaryl,aralkyl.or cyclicnonsroups. Theorganicsro p msybeeltherdirectlsatiachedtothe atom oi the compound or attached thereto thmlghanatomsuchasm .'1hetermoxyacldsotphosphomsisint endedto deslgnatethroushmit acidsoi phosphorus inwhichoneoxygenatom mayintervenebetweenthehydroaenandphoaphorusatomsottheester. V

Thepreienedacidsaresubstituted orthcphos- 15 nesiumcetvl Dh 'nyl phosphate, masneslma di- 7 naphtbenvl Phosphate, barium di-cyclohezangi phosfhate, barium um" I I -n (d-chloro, z-phenyl phcuyD-phosphate, and 111m t yl. 4m li l!!!) phosphate.

Thesubstitutedoxyaddsoiuflliad inthepresentinventionmaybemr dby methodsknownintheart. l ar-examplesmixuueoi'ahigheralcoholaudpentoxldeinethylethermaybereiluxed iorseveral hours. 'lhereactionbywhlchthembstituted phosphoricacldisiormedinthisopesationlsbslievedtoberemtedbythciollo'wingequa tion. noa+cimocim+m ac=mm+csm whereRlsanalkylradical. 'lhealkyletbslphos Dhorlcacid is solublein ether'whil the ethyl metaphcsphate is not. and the ether soluticn'ot the-iormermaybeiromthelatterhy decantatiom. Table 1 gives anumberot-examples aluminum osphate magneshun fa. sncslum di-(B- substituted phobhorlc acids suitable for the s,ssa,oaa

purposes or this invention and a brief indication preparation.

as to their method of TAIL! 1 Acid Method of preparation 9.25 lb. eetyl alcohol and 5.61 lb. P305 were refluxed with gal. ethyl ether (or 24 hr. Cetyl-phosphoric acid solution decanted.

112 gms aolid' sperm alcohols oi l gms. an gms. e y ether as above.

100 gms. octsdecsnol and 150 cc. benumetreatedwith 56.8 gins. P001. Product was hydrolyzed to give a free acidic hydrogen.

100 gm. of the phenol and 50 gins.

PiOr heated to 181 for 18 hr.

Mono-oetylphosphoric Mom-spermol" phosphoric- Mouo-octsdecylphosphorio Di-(0-chloro-2-phenylphenyi) phosphoric Mono-oleyl hosphoric. 107 gms. ole 1 alcohol and 28.5 gms. p P10. were redussd in ethyl ether for 24 hours. Mono-spermsn l hos- 107 gms. liquid sperm alcohols and phorie. y p 2'] ms. P; refluxed in ethyl ether (or 24 Dicyclohexsn l hos horic.-. 150 oycloheranol and 87 gms. y p p Pa f refluxed with 150 gms. ethyl other for 24 hr. (Cetylphenyl) phosphoric--. 088 gms. cetyl phenol and 310 gms.

P 0; refluxed with ethyl ether for 24 hr.

DHsmylphenol) phosphoric. 100 gms. amyl phenol and gms.

Pr s haatcd'to 185 F. for hr.

Monotetrschloro octadeeyl 100 gms. tetrachloro-oetademnol and phosphoric 28 gms. Pi0| refluxed with ethyl ether for 17 hr.

or potassium hydroxide and then precipitating the desired metal salt from the solution 01' the sodium or potassium salt by the addition 01'- the appropriate metal ion. The salt may also be prepared by the direct neutralization of the acid as, for example, with lime where the calcium salt is to be obtained.

- Basic aluminum salts prepared by the precipitation method are preferred by reason of their low corrosivity to alloy bearing metals although the so-called normal salts are not precluded. It is also preferred to maintain the amount of coprecipitated alkali metal salt in the heavy metal compounds at a minimum because the alkali meta! salts decrease the stability of theoil solution in the presence of water.

I The calcium salts may also be prepared in the nonaqueous environment by the reaction of calcium carbide with the free substituted acids of phosphorus.

The aluminum salts may also be prepared in an environment substantially free of water by the reaction of aluminum chloride with the free substituted acids of phosphorus. However. such aluminum salts have properties dinerent from the salts prepared by precipitation from aqueous solutions. The salts prepared in a nonaqueous environment are soft, low melting solids, while the corresponding salts prepared by precipitation from aqueous solutions are hard nonmelting solids. Although the former type of salt may be utilized for imparting some desirable properties to hydrocarbon oils. it is preferred to use a salt prepared by precipitation from aqueous solutions where the ability to inhibit piston ring sticking in lubricating oils is desired.

By way of illustration and to demonstrate the unique properties possessed by. the compounded oils of this invention, data from extensive tests pared by reacting the acid with sodium hydroxide are given in Table 2.

. TABLI 2 Miscellaneous tests Engine tests, Lauson Strip corrosion B Preparation 01 compound Com d 1am: Ring Cleanii 0 Pb 1 Cd A l l lm mtg? pared sticking nesa u a F. Add from- Add treated western oiL. 0 1.0 Poor 1.0 Aluminum lsuryl phos- 1.0 5.0 Good 0. 1 Commercial lauryi phos- Na salt.

phase. phoric acid.

Do 0.05 0.1, do Do. Aluminum cetyl phos- 1.0 5.0 Very good. Get 1 alcohol Pr0s+ Do.

e or. 0.1 4.0 ('icod 0.2 o Do.

ate.

um "spormo 1.0 5.0 do Low 4.0 Solid sperm sioohols+ Do.

phosphate Pa0s+othen Do 0.7 6.0 do 1.0 1.0 211 (in p Aluminum oleyl phos- 0.7 4.0 Good 0.1 1.0 ou l alcohol P10. Do.

Amnm sparmenyr' 0. 3 2.0 Fair..... 0. 1 02 Liquid sperm alcohol+ Do.

phste. Prod-other.

Amino: di-cyclohex- 0. 1 5.0 Veryg Oyel '1 P505 Do.

snyl phosphate. other.

Aluminum h di-(amyl- 1.0 3.0 Fair 0.5 2.0 I 131 Amyiphenol+P10 Do.

"(fit-Wye- 0.7 2.0 do Glyceryl distearate+ Do.

hosphste. a er. 5.

Ag ir mm tetra-chloro- 0. 1 3:1; 0.2 3.0 mi ait rrsmictsdecanol Do.

oetsdecyl hate. r l or.

Calcium lsuryl phosl.0 2.0 .do 1.0 5.0 451 Comdlauryl phos- Do.

0% cetyl phosphate. 0.5 5:: Excellent Ostyl alcohol+P|0s+ K salt.

ether.

............. 0.9 as: 7' good. 0.5 1.0 162 0.33 (in oetyl phos- 0.8 0.3 0.2 220 do Na salt. m": I 1.0 so do do Do.

Magnesium huryl phor 1.0 2.0 Fsir. 9.0 40.0 401 Comrcialdlauryl phos- Do.

. p A uminum W71 phol- 0.3 1.0 do 0-1 0.5 $4 Lsuryl alooho1+POl|--'.-- Do.

ph I

1 E prened tin of time to stick rin oi compounded oil to that with an uncompounded Western acid refined oil SAE 3). E;pressed:s r :tiooicom edoil ntooorrosionwithWesternscidreilnodoilBAEiiO.

I Espremed as ratiooi wear of compoundedoil to that 0! Westemacidrefined oil SAE 30. Thsbsssoilussdlortsstiugthesdditionssuitwssinsllesslmseidnflnsdwntcnoilflalilsrsde.

4- V assaosa extremely low wearrates'were obtained with the two compounded oilstestedintheweeks ma-' chine. Allolthe additionagentsimprovedpiston cleaniinessandimpartedresistancetopistonring stickinginenginetests.

Intheabovepistonringsflckingtestsasingle cylinder 2% inch bore, z b'incb stroke Lauson gasolineenginewasoperatedimderextremelyse- .vereconditionsforthepurposeotde'veloping iuliymstonrihgstlckingandpistongumming tendencies under circumstances simulating se- '15 vere operating conditions encountered in the fleld. Operation of the motor duringtests was conflnuous at 1600 R. P. H. except for shut-v downs atiiiteen-hour intervals for The jacket temperature was maintained at 375 1'. and the sump oil temperature at220" 1". Theweartestswerecarrledoutinaweeks machinecomprisingatiinchsteelball againstallfiinchsteelclrlinderwithaforceot 40lbs.,thecylinderdipl l 8iniheoiltobetested androtatingatwORRH. Theduratlonof thetestwassixteenhoursandthewearraiedeterminedbytheamountotmetalremovedfromtheball. Inthe aboveweartests' the lubricant was maintained at approximately 3o 300 F. as indicated.

Thecorrosiontestswerecan'ledoutinthe lollowing manner: Glass tubes 2 inchesindiameter andmin'cheslongwereimmersedinanoilbath,

t e temperature of which was automatically eontrolled to within i-1 1". of he test temperature which was 300' 1'. Approximately 300 cc. of oil underthetestwasplacedin'eachtube andairwas bubbled through it at the rate of 10 liters per hour. Strips of the diiierent types of bear- 40 mg metalswerecuttosiaeandplacedintheoils; inmostcasesthecopper-leadmixtureandcadmium-silver bearing alloys were tested simultaneouslyinthe samesample oioil. Theweightloss of eacbstrip was recorded. Before weighing, each strip was washed in petroleum ether and carefully wiped with asoi't cotton cloth. The duration of the test'was '12 hours. 7

To further illustrate the corrosion inhibiting properflesoitheoompoundingaz l d closed,theiol1owingdataobtainedintheabove. marzi an-mammalian:

Tamil 3 utilised-and the environment which the lubricatingoillstoencolmter. Itshouldbeobserved. I lnits broader-aspects embraces mineral hydr for example, that even though a compounded oil may be somewhat corrosive to copper-lead or cadmium-silver bearing metals, Babbitt bearings are little if at all affected by such corrosive action. Hence, compwndedoils whichmaynotbe particularly desirable for lubrication 01' copperlead or cadmium-silver bearings may be highly useful and extremely advantageous in' conjunction with theoperationofinternal engines having bearings of Babbitt or other corrosive-resistant bearing metals. lhe present invention in its broader aspects is therefore not limited totheuseoiaparticularcompoundhavingall or the greatest number of advantages, but embraces various of the less advantageous addition agents which will iind utility in particular applications where all the possible improvement in properties may not be required or where the standard oi-performance may not be so high.

Present experience indicates that where the properties desired involve the ability to stabilise lubricating oils under severe operating conditions, suchasthose encmmteredinthelubricationoi pistonsandpistonringsofinternalcomlmstion engines or the Diesel type, polyvalent metal suit 0! substituted oxyacids or pentavalent phosphorus containing more than twelve carbon atoms in the molecule and preferably containing an alkyl or alkaryl substituent should be utilised. ltistobeunderstoodthatbywolyvalentmetal salts" used in the above connection the alkaline earth metals are included.

A moderately acid refined western naph baseoilisthe prei'erredoilstockusedasabase for the compounded lubricants involved herein. The compounding ingredients appear to function moreeilicientlyinsuchabaseoilthaninahighly .paraiflnic oil stock 01' a hizhly refined Western 011. However, it is to be understood that the invention is not limited to any particular base stocksince advantages herein disclosed may be The proportion of metal salts of substituted onacids or phosphorusaddedio mineral lubricating oils may vary widely depending upon the usesinvolvedandthedesired. Aslittle 850.05% byweightoftheoompmmdgivumeasurable improvementaparticularlyurespectstbe coloroi'thecompoundedoilaiteruseininternal combustion engines. From approximately 0.35 toapproximately 2% of the compound may be 'added to lubricants where ability to inhibit pistonringsflckingtheprlncipalmy' desired. Solutions containing more than 2%01' theinmiheraloilma'ybeutiliaedior the'purposeofpreparinglubricatingareasuand concentrates capable of dilution with lubricating,

oils and the like; Suchjhigher concentrations comprise a convenient-mowed of handling compounds andmay be used as addiflon agents for lubricants ingeneral as well as for other The metal salts oi this invention may be added to hydrocarbon oils containing other compolmdingingredients such as pour point depressors, oiliness agents, extreme pressure addition agents, blooming agents, compounds to;- enhansing the viscosity index of the hydrocarbon oil, corrosion inhibitors, colorstabilizers, etc. 1 The invention carbon oils containing, in addition to metal salts or the substituted acids of phosphorus, thickening agents and/or metal soaps in grease-forming no limitation should be imposed on the inven-' tion thereby. It will be apparent to those skilled in the art that numerous modifications and variations of the illustrative examples may be efltected in the practice of the invention which is of the scope. of the claims appended hereto.

We claim:

1. A lubricating composition comprising 'a hydrocarbon nil subject to deterioration at elevated temperatures and a small amount, suflicient to inhibit said deterioration, of a polyvalent metal salt of an acid of pentavalent phosphorus having an organic radical directly attached to a phosphorus atom of said acid by a carbon-to-phosphorus bond.

2. A composition comprising a hydrocarbon oil and from approximately .05% to 2% by weight based on the oil of a polyvalent metal salt of an. acid of pentavalent phosphorus having an organic radical directly attached to a phosphorus atom of said acid by a carbon-to-phosphorus bond.

3. A composition comprising a hydrocarbon oil and from approximately 05% to 2% by weight carbon-to-phosphorus bond and selected from the class consisting of the types monoestcr of pbosphonic acid phosphonic acid phosphinic acid II R 0 in which R and R may be alkyl, aryl, alkaryl, aralkyl or cyclic nonbenzenoid groups.

6. A liquid lubricating composition comprising a hydrocarbon oil subject to deterioration at elein which R may be an alkyl, aryl, alkaryl, aralkyl or cyclic nonbenzenoid group. a

7. A liquid lubricating composition comprising a hydrocarbon oil subject to deterioration at elevated temperatures and a small amount, suflicient phosphonic acid to inhibit said deterioration, of a polyvalent metal based on the oil of a polyvalent metal salt of an acid of pentavalent phosphorus having an organic radical directly attached to a phosphorus atom of said acid by a carbon-to-phosphorus bond.

4. A liquid lubricating composition comprising a hydrocarbon oil subject to deterioration at elevated temperatures and a small amount, suflicient to inhibit said deterioration, of a polyvalent 'salt of a substituted acid of pentavalent phosphorus represented by the typ formula I OH monoester of phosphonic acid in which R and R' may be alkyl, aryl, alkaryl,

to inhibit said deterioration, of a polyvalent metal Salt of a substituted acid of pentavalent phosphorus represented by the type formula PQH phosphinic acid II R O in which R and R may be alkyl, aryl, alkaryl,

aralkyl or cyclic nonbenzenoid groups.

BRUCE B. FARRINGTON. JAMES O. CLAYT QNJ JOHN T. RUTHERFORD. 

